Abstract

The process of phenol oxidation on a boron-doped diamond electrode (BDD) is studied in acidic electrolytes under different conditions of generation of active oxygen forms (AOFs). The scheme of phenol oxidation known from the literature for other electrode materials is confirmed. Phenol is oxidized through a number of intermediates (benzoquinone, carboxylic acids) to carbon dioxide and water. Comparative analysis of phenol oxidation rate constants is performed as dependent on the electrolysis conditions: direct anodic oxidation, with oxygen bubbling, and addition of H2O2. A scheme is confirmed according to which active radicals (OH·, HO2·, HO2−) are formed on a BDD anode that can oxidize the substrate which leads to formation of organic radicals interacting with each other and forming condensation products. Processes with participation of free radicals (chain-radical mechanism) play an important role in electrochemical oxidation on BDD. Intermediates and polymeric substances (polyphenols, quinone structures, and resins) are formed. An excess of the oxidant (H2O2) promotes a more effective oxidation of organic radicals and accordingly inhibition of the condensation process.

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